WO2021066550A1 - 하이드록시기 함유 화합물을 이용한 폴리알킬알루미녹산 함유 용액의 정제방법 및 이를 이용한 촉매 조성물 - Google Patents
하이드록시기 함유 화합물을 이용한 폴리알킬알루미녹산 함유 용액의 정제방법 및 이를 이용한 촉매 조성물 Download PDFInfo
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- WO2021066550A1 WO2021066550A1 PCT/KR2020/013380 KR2020013380W WO2021066550A1 WO 2021066550 A1 WO2021066550 A1 WO 2021066550A1 KR 2020013380 W KR2020013380 W KR 2020013380W WO 2021066550 A1 WO2021066550 A1 WO 2021066550A1
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- aluminum
- polyalkylaluminoxane
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- compound
- hydroxy group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/52—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from boron, aluminium, gallium, indium, thallium or rare earths
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/602—Component covered by group C08F4/60 with an organo-aluminium compound
- C08F4/6028—Component covered by group C08F4/60 with an organo-aluminium compound with an alumoxane, i.e. a compound containing an -Al-O-Al-group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
- C08F4/61912—Component covered by group C08F4/60 containing a transition metal-carbon bond in combination with an organoaluminium compound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2420/00—Metallocene catalysts
- C08F2420/02—Cp or analog bridged to a non-Cp X anionic donor
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2420/00—Metallocene catalysts
- C08F2420/06—Cp analog where at least one of the carbon atoms of the non-coordinating part of the condensed ring is replaced by a heteroatom
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2420/00—Metallocene catalysts
- C08F2420/07—Heteroatom-substituted Cp, i.e. Cp or analog where at least one of the substituent of the Cp or analog ring is or contains a heteroatom
Definitions
- the present invention relates to a method for purifying a solution containing polyalkylaluminoxane using a hydroxy group-containing compound, a method for preparing a catalyst composition using the same, a catalyst composition prepared by the method, and a method for preparing an olefin polymer using the same.
- the polyalkylaluminoxane composition which is a partial hydrolyzate of alkylaluminum, acts as a cocatalyst or scavenger to activate the main catalyst in the manufacture of an olefin polymer.
- a scavenger is a substance added to the catalyst system to react with impurities present in the polymerization reactor, solvent, and monomer feed, and plays a role of preventing poisoning of the catalyst during the polymerization process of olefinic monomers through reaction with the impurities. do.
- scavenger various types of compounds such as trialkyl aluminum, alkyl aluminoxane, dialkyl zinc, and dialkyl magnesium are used, and examples include polymethylaluminoxane and polyisobutylaluminoxane as described above. have.
- Polyalkylaluminoxane one example of a scavenger, is commercially available as a solution dissolved in a hydrocarbon solvent such as toluene, and it is purchased and used in a polymerization reaction when necessary.
- the commercially available polyalkylaluminoxane solution contains trimethylamine (TMA), triisobutylaluminum (Tibal), etc. in addition to the polyalkylaluminoxane as the main component.
- TMA trimethylamine
- Tibal triisobutylaluminum
- TMA and Tibal react with the transition metal compound acting as a main catalyst to reduce the catalytic activity of the transition metal compound, thereby interfering with the formation of the olefin polymer, or participating in the polymerization reaction to act as a chain transfer agent, thereby creating a high molecular weight olefin polymer. Make it impossible to manufacture.
- the purchased composition solution is 2,6-di-tert-butyl-4-methylphenol (2,6-di-tert-butyl-4 -Methylphenol; BHT) by reacting with the aluminum element of Tibal to bind the BHT, a method of preventing the additional reaction of Tibal is known.
- BHT 2,6-di-tert-butyl-4-methylphenol
- An object of the present invention is to provide a method for preparing a catalyst composition by reacting a polyalkylaluminoxane-containing solution with a hydroxy group-containing compound, followed by filtration and purification, and mixing it with a transition metal compound.
- Another object of the present invention is to provide a catalyst composition using a polyalkylaluminoxane-containing solution containing a small amount of trialkylaluminum.
- Another object of the present invention is to provide a method for producing an olefin polymer using the catalyst composition.
- the present invention comprises the steps of (S1) preparing a polyalkylaluminoxane-containing solution comprising a polyalkylaluminoxane, a trialkylaluminum, and a hydrocarbon solvent; (S2) reacting the polyalkylaluminoxane-containing solution with a hydroxy group-containing compound; (S3) filtering the reaction product of step (S2); And (S4) mixing the filtrate of step (S3) with the transition metal compound.
- the present invention is a polyalkylaluminoxane-containing solution containing a polyalkylaluminoxane, trialkylaluminum and a hydrocarbon solvent; And a transition metal compound, wherein the trialkylaluminum provides a catalyst composition of 4.3 mol% or less based on a solution containing polyalkylaluminoxane.
- the present invention provides a method for producing an olefin polymer comprising; polymerizing an olefin-based monomer in the presence of the catalyst composition.
- a commercially available solution containing polyalkylaluminoxane can be purified to remove trialkylaluminum present in the solution, and when it is used as a catalyst composition, the polymerization reaction is prevented from being disturbed by the trialkylaluminum.
- the activity of the main catalyst compound can be maximized and an olefin polymer can be efficiently produced.
- the method for preparing the catalyst composition of the present invention comprises the steps of: (S1) preparing a polyalkylaluminoxane-containing solution comprising a polyalkylaluminoxane, a trialkylaluminum, and a hydrocarbon solvent; (S2) reacting the polyalkylaluminoxane-containing solution with a hydroxy group-containing compound; (S3) filtering the reaction product of step (S2); And (S4) mixing the filtrate of step (S3) with the transition metal compound.
- the step (S1) is a step of preparing a polyalkylaluminoxane-containing solution containing polyalkylaluminoxane, trialkylaluminum, and a hydrocarbon solvent.
- the preparation of the polyalkylaluminoxane-containing solution may be included in the present invention regardless of the method or route of obtaining it, but may specifically mean obtaining and preparing a commercially available polyalkylaluminoxane-containing solution.
- commercially available polyalkylaluminoxanes are all sold as a solution dissolved in a hydrocarbon solvent, and contain more than a certain amount of trialkylaluminum, which causes a problem of lowering the catalytic activity of the main catalyst when participating in the polymerization reaction.
- An object of the present invention is to purify the trialkylaluminum contained in the polyalkylaluminoxane-containing solution prepared in step (S1) so that it can be more usefully used in the production of an olefin polymer.
- the polyalkylaluminoxane may be added as a material that serves as a scavenger, a cocatalyst, or both in the catalyst composition.
- the polyalkylaluminoxane may be one or more selected from the group consisting of polymethylaluminoxane, polyethylaluminoxane, polyisobutylaluminoxane, and polybutylaluminoxane, and may be, for example, polyisobutylaluminoxane, but is not limited thereto. Does not.
- the trialkyl aluminum is trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloro aluminum, triisopropyl aluminum, tri-s-butyl aluminum, tricyclopentyl aluminum, tripentyl aluminum, Triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyldimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, and tri-p-tolyl aluminum may be at least one selected from the group consisting of aluminum, preferably triisobutyl aluminum May be, but is not limited thereto.
- the hydrocarbon solvent is 1 selected from the group consisting of aliphatic hydrocarbon solvents including pentane, hexane, heptane, nonane, decane, cyclohexane, and isomers thereof, and aromatic hydrocarbon solvents including toluene, benzene, xylene, and isomers thereof.
- aliphatic hydrocarbon solvents including pentane, hexane, heptane, nonane, decane, cyclohexane, and isomers thereof
- aromatic hydrocarbon solvents including toluene, benzene, xylene, and isomers thereof.
- the step (S1) may be a step of preparing a mixed solution containing polyisobutylaluminoxane, triisobutylaluminum, and hexane.
- the content of the hydrocarbon solvent contained in the polyalkylaluminoxane-containing solution may be 20 to 99% by weight based on the polyalkylaluminoxane-containing solution.
- the content of the hydrocarbon solvent is less than 20% by weight, as described below, the insoluble solids produced by the reaction of the polyalkylaluminoxane-containing solution and the hydroxy group-containing compound are entangled with each other, making it difficult to stir. Since it may be difficult to implement the effect of the present invention to remove the trialkylaluminum in the containing solution, a sufficient amount of a hydrocarbon solvent is required.
- the step (S2) is a step of reacting the polyalkylaluminoxane-containing solution with a hydroxy group-containing compound.
- the method of reacting the polyalkylaluminoxane-containing solution with the hydroxy group-containing compound is to add a hydroxy group-containing compound to the polyalkylaluminoxane-containing solution prepared in step (S1), for example, a hydroxy group-containing compound in a slurry state. It can be made by a method of transferring to a solution containing polyalkylaluminoxane. In addition, it may be achieved by adding a polyalkylaluminoxane-containing solution to the hydroxy group-containing compound. As long as the polyalkylaluminoxane-containing solution and the hydroxy group-containing compound can be brought into contact with each other to react, the order or speed of mixing of each substance is not limited, and a person skilled in the art can appropriately control it.
- a solid product is prepared by reacting trialkylaluminum and a hydroxy group-containing compound in a mixed solution of a polyalkylaluminoxane-containing solution and a hydroxy group-containing compound. It may be insoluble in hydrocarbon solvents.
- the insoluble solid is a non-hazardous substance that is stable in air and does not burn or generate combustible substances, unlike trialkyl aluminum, which is classified as a third class dangerous substance as a pyrophoric and non-aqueous substance.
- trialkyl aluminum since the trialkyl aluminum was not only efficiently removed, but also the dangerous trialkyl aluminum was transformed into a non-hazardous material, it is more preferable than the method of physically separating trialkyl aluminum or aluminoxane by itself.
- the hydroxy group-containing compound may be 100 equivalents or less based on 1 equivalent of trialkylaluminum contained in the polyalkylaluminoxane-containing solution.
- the hydroxy group-containing compound may be 0.01 to 100.00 equivalents based on 1 equivalent of trialkylaluminum contained in the polyalkylaluminoxane-containing solution, 0.01 equivalents or more, 0.05 equivalents or more, 0.10 equivalents or more, 1.00 equivalents or more, 100.00 It can be used in equivalents, 50.00 equivalents or less, and 10.00 equivalents or less.
- the amount of the hydroxy group-containing compound is less than 0.01 equivalent, the effect of removing trialkyl aluminum may be insignificant due to insufficient reaction with the trialkyl aluminum, and when the hydroxy group-containing compound is more than 100 equivalents, the hydroxy group-containing compound Since the removal efficiency of trialkyl aluminum does not increase as much as the amount of the trialkyl aluminum, economical efficiency may be lowered, and due to excessive generation of insoluble solids, they become entangled with each other, and it may be difficult to stir and filter.
- the hydroxy group-containing compound refers to a compound containing one or more hydroxy groups, and specifically, a compound having 2 to 60 carbon atoms containing two or more hydroxy groups, and preferably two carbon atoms containing two or more hydroxy groups. It may be a compound of to 30. As described above, a hydroxy group-containing compound containing two or more hydroxy groups may be preferably used because it can more efficiently react with trialkyl aluminum.
- the hydroxy group-containing compound has a low solubility in an organic solvent such as hexane, it is highly likely that the material combined with the trialkylaluminum is solidified, so that the effects of the present invention can be more excellently implemented.
- the hydroxy group may be substituted on an aromatic ring and may be bonded to a hydrocarbon chain, and if there are two or more aromatic rings, each may be substituted on different aromatic rings or all substituted on one aromatic ring. , Is not limited thereto.
- hydroxy group-containing compound examples include 1,3,5-trihydroxybenzene, neopentyl glycol, naphthalene-1,5-diol, ethylene glycol, bisphenol-A, catechol, methylhydroquinone, and 1,2 It may be one or more selected from the group consisting of ,3-trihydroxybenzene, but is not limited thereto.
- the step (S3) is a step of filtering the reaction product of the step (S2), and the insoluble solid produced by the reaction of the trialkyl aluminum and the hydroxy group-containing compound in the previous step (S2) is mixed by filtering using a filtration membrane. This is the step of removing from the solution.
- the filtration may be performed with a pore size of 0.1 to 40.0 ⁇ m, specifically 0.10 ⁇ m or more, 0.15 ⁇ m or more, 0.20 ⁇ m or more, 1.0 ⁇ m or more, 5.0 ⁇ m or more, 7.0 ⁇ m or more, 40.0 ⁇ m or less, 35.0 ⁇ m or less, 30.0 It may be performed using a filtration membrane of ⁇ m or less, 20.0 ⁇ m or less, 15.0 ⁇ m or less, for example, 10 ⁇ m.
- the insoluble solid produced by the reaction of the trialkyl aluminum and the hydroxy group-containing compound may block the pores of the filtration membrane, thereby reducing filtration efficiency and lengthening the filtration time.
- the insoluble solid may pass through the filtration membrane, resulting in failure to separate and remove it.
- a filtration membrane having a pore size within a range capable of efficiently removing the solid produced in step (S2) can be appropriately selected and used, through which a solution containing high purity polyalkylaluminoxane from which trialkylaluminum has been effectively removed is prepared. It can be obtained.
- step (S3) the reaction product of step (S2) may be directly filtered, or the reaction product of step (S2) is allowed to stand to precipitate an insoluble solid, and then only the supernatant is recovered and filtered. As described above, only the supernatant may be recovered and filtered to first remove a large amount of insoluble solids, thereby increasing the efficiency of removing the insoluble solids.
- the method for preparing the catalyst composition of the present invention physically removes the trialkyl aluminum contained in the polyalkylaluminoxane-containing solution through the steps (S1) to (S3), so that the trialkylaluminum in the solution is 4.3 mol%. It may be reduced to the following, and the content of trialkyl aluminum may be further lowered depending on the reaction conditions, types of polyalkylaluminoxane and trialkylaluminum, pore size of the filtration membrane, and the like.
- the step (S4) is a step of mixing the filtrate of step (S3) and the transition metal compound.
- a solution was obtained in which the relative content of polyalkylaluminoxane was increased and the content of impurities such as trialkylaluminum was decreased through steps (S1) to (S3).
- a catalyst composition is prepared by mixing a transition metal compound serving as a main catalyst through step (S4).
- the catalyst composition thus prepared contains polyalkylaluminoxane, which is used as a scavenger and/or a cocatalyst, and at the same time is not disturbed by trialkylaluminum, so that the catalytic activity of the transition metal compound can be remarkably improved.
- the catalyst composition of the present invention includes a polyalkylaluminoxane-containing solution containing a polyalkylaluminoxane, a trialkylaluminum, and a hydrocarbon solvent; And a transition metal compound, wherein the trialkyl aluminum is not more than 4.3 mol% based on a solution containing polyalkylaluminoxane.
- the catalyst composition may be obtained through the production method of the present invention.
- the catalyst composition is prepared by removing trialkyl aluminum in a polyalkylaluminoxane-containing solution according to the present invention and then mixing it with a transition metal compound, and the trialkylaluminum contained in the polyalkylaluminoxane-containing solution is 4.3 mol% or less. It is a low content of.
- the catalyst composition includes polyalkylaluminoxane and a transition metal compound (main catalyst compound), and may further include one or more cocatalyst compounds.
- the catalyst composition refers to a state in which the three components of a transition metal compound, a cocatalyst compound, and a polyalkylaluminoxane are mixed simultaneously or in any order, thereby obtaining an active composition.
- the transition metal compound may be any compound known to function as a catalyst in the polymerization reaction of an olefinic monomer.
- the cocatalyst may include at least one selected from Formula 1 or 2 below, but is not limited thereto.
- Each R 1 is independently a halogen radical; A hydrocarbyl radical having 1 to 20 carbon atoms; Or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with a halogen,
- L is a neutral or cationic Lewis acid
- H is a hydrogen atom
- Z is a group 13 element
- A is each independently an aryl group having 6 to 20 carbon atoms in which one or more hydrogen atoms may be substituted with a substituent; Or at least one hydrogen atom is an alkyl group having 1 to 20 carbon atoms which may be substituted with a substituent,
- the substituent of A is a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms.
- the compound represented by Formula 1 may include, but is not limited to, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, and the like.
- Examples of the compound represented by Formula 2 include trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tributylammonium tetraphenylborate, trimethylammonium tetra(p-tolyl)borate, triethylammonium Tetra(p-tolyl)borate, tripropylammonium tetra(p-tolyl)borate, tributylammonium tetra(p-tolyl)borate, trimethylammonium tetra(o,p-dimethylphenyl)borate, triethylammonium tetra(o, p-dimethylphenyl)borate, tripropylammonium tetra(o,p-dimethylphenyl)borate, tributylammonium tetra(p-toly
- the catalyst composition is obtained by contacting a transition metal compound with a compound represented by Formula 1 to obtain a mixture; And adding a compound represented by compound 2 to the mixture.
- the molar ratio of the compound represented by Formula 1 based on the transition metal compound may be 1: 2 to 1: 5,000, preferably 1: 10 to 1: 1,000, more preferably 1: 20 to 1: 500 Can be
- the amount of the alkylating agent is very small, so that the alkylation of the metal compound does not proceed completely.
- alkylation is performed, there is a problem in that activation of the alkylated metal compound is not completely achieved due to a side reaction between the remaining excess alkylating agent and the activating agent, which is a compound represented by Formula 2 above.
- the catalyst composition may be prepared by a manufacturing method including a step of contacting a transition metal compound with a compound represented by Formula 2 above.
- the molar ratio of the compound represented by Formula 2 based on the transition metal compound may be 1:1 to 1:25, preferably 1:1 to 1:10, more preferably 1:1 to 1: May be 5.
- the amount of the activator is relatively small, so that the activation of the metal compound is not fully achieved, and thus the activity of the resulting catalyst composition decreases, If it exceeds 1:25, activation of the transition metal compound is completely achieved, but there is a problem that the unit cost of the catalyst composition is not economical or the purity of the resulting polymer is poor with the excess amount of the remaining activator.
- a hydrocarbon-based solvent such as pentane, hexane, heptane, etc., or an aromatic solvent such as benzene, toluene, etc. may be used as the reaction solvent.
- a hydrocarbon-based solvent such as pentane, hexane, heptane, etc.
- an aromatic solvent such as benzene, toluene, etc.
- the catalyst composition provided in the present invention is It is excellent in the activity of accelerating the polymerization reaction, and by using it, it is possible to prepare an olefin polymer in good yield.
- trialkyl aluminum was permanently removed from the solution containing polyalkylaluminoxane by filtration by converting it into a solid product, there is no fear of any problems such as reverse reaction and trialkylaluminum re-existing in the solution.
- the stability and predictability of the reaction can be further improved.
- the method for producing an olefin polymer of the present invention is characterized by including a step of polymerizing an olefin-based monomer in the presence of the catalyst composition.
- polymer refers to a polymer compound prepared by polymerizing monomers of the same or different types.
- the generic term polymer thus encompasses the term homopolymer, which is commonly used to refer to a polymer made from only one monomer, and the term interpolymer as defined below.
- the olefinic monomers are ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene , 1-tetradecene, 1-hexadecene, and 1-eicosene may be one or more selected from the group consisting of, but is not limited thereto.
- the olefin polymer of the present invention may be an olefin homopolymer, an olefin/alpha-olefin copolymer, and preferably an ethylene/alpha-olefin copolymer, depending on the type of the olefin-based monomer.
- the content of the alpha-olefin-based monomer as a comonomer may be appropriately selected by a person skilled in the art depending on the use and purpose of the olefin polymer, and may be about 1 to 99 mol%.
- the most preferred polymer production process using the catalyst composition is a solution process, and if the catalyst composition is used together with an inorganic carrier such as silica, it can be applied to a slurry or gas phase process.
- the catalyst composition is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms suitable for the polymerization process of an olefinic monomer, such as pentane, hexane, heptane, nonane, decane, and isomers thereof, and an aromatic hydrocarbon solvent such as toluene and benzene, and dichloromethane. , It can be dissolved or diluted in a hydrocarbon solvent substituted with a chlorine atom such as chlorobenzene and injected.
- the solvent used here is preferably used after removing a small amount of water or air acting as a catalyst poison by treatment with a small amount of alkyl aluminum, and it is possible to further use a cocatalyst.
- Polyisobutylaluminoxane (PBAO) was purchased from Tosho and used as it was dissolved in hexane.
- the solution containing polyisobutylaluminoxane purchased from Tosho contains 4.4 mol% of triisobutylaluminum.
- the hydroxy group-containing compound was purchased and used from Aldrich or TCI, respectively.
- the mixture was stirred for 12 hours and allowed to stand to form a solid product, and then allowed to stand overnight. While still standing, the supernatant portion was carefully filtered using a 10.0 ⁇ m pore size filter.
- the solution containing polyalkylaluminoxane was used as purchased from Tosho.
- Example 1 in the case of Example 1 using a filtration membrane having a pore size of 10.0 ⁇ m while using 1,3,5-trihydroxybenzene based on 2.00 equivalents of triisobutylaluminum, triisobutyl for a short time By selectively removing aluminum, the filtration time was shortened and the recovery rate was also excellent.
- Example Preparation 3 using a filtration membrane having a pore size of 0.15 ⁇ m the filtration time was increased, and in Example Preparation Example 4 using a filtration membrane having a pore size of 35.0 ⁇ m, it was observed visually that a part of the insoluble solid was filtered together.
- a transition metal compound of the following formula (A) was prepared using the manufacturing method disclosed in Korean Patent Registration No. 10-0738694.
- a transition metal compound of the following formula (B) was prepared using the manufacturing method disclosed in Korean Patent Laid-Open Publication No. 10-2016-0019875.
- An olefin polymer was prepared in the same manner as in Example 1, except that the compound of Formula B was used as the transition metal compound.
- An olefin polymer was prepared in the same manner as in Example 1, except that the polyalkylaluminoxane-containing solution of Comparative Preparation Example 1 was used instead of Preparation Example 1.
- An olefin polymer was prepared in the same manner as in Example 2, except that the polyalkylaluminoxane-containing solution of Comparative Preparation Example 1 was used instead of Preparation Example 1.
- the catalytic activity was calculated by dividing the obtained polymer by the number of moles of the transition metal compound used in the polymerization reaction.
- a sheet having a thickness of 3 mm and a radius of 2 cm was prepared in a 180° C. press mold, cooled at 10° C./min, and measured on a Mettler scale.
- the melting temperature of the polymer was measured using a differential scanning calorimeter (DSC, device name: DSC 2920, manufacturer: TA instrument). Specifically, the polymer was heated to 150° C. and maintained for 5 minutes, and the temperature was lowered to -100° C., and then the temperature was increased again. At this time, the rate of rise and fall of the temperature were each adjusted to 10 °C/min. The melting temperature was taken as the maximum point of the endothermic peak measured in the section where the second temperature rises.
- DSC differential scanning calorimeter
- Example 1 and Comparative Example 1 and Example 2 and Comparative Example 2 having the same type of the transition metal compound
- the transition metal compound was the same, but the polyisobutylaluminoxane-containing solution was mixed with the hydroxy group-containing compound.
- Examples 1 and 2 used by removing triisobutyl aluminum by reacting it was found that the catalytic activity was three or more times higher than that of Comparative Examples 1 and 2, respectively.
- the catalyst composition prepared by the production method of the present invention can increase the catalytic activity of the transition metal compound and efficiently prepare an olefin polymer, which is implemented in various types of transition metal compounds regardless of the type of the transition metal compound. It was confirmed that it was effective.
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CN202080058203.XA CN114269795B (zh) | 2019-09-30 | 2020-09-29 | 使用含羟基化合物纯化含聚烷基铝氧烷溶液的方法和使用该方法的催化剂组合物 |
US17/634,721 US20220275113A1 (en) | 2019-09-30 | 2020-09-29 | Method for Purifying Polyalkylaluminoxane-Containing Solution Using Hydroxy Group-Containing Compound and Catalyst Composition Using the Same |
EP20871977.3A EP4001314A4 (de) | 2019-09-30 | 2020-09-29 | Verfahren zur reinigung von polyalkylaluminoxan unter verwendung einer hydroxygruppenhaltigen verbindung und katalysatorzusammensetzung unter verwendung derselben |
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EP (1) | EP4001314A4 (de) |
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KR20110094301A (ko) * | 2008-11-11 | 2011-08-23 | 토소 화인켐 가부시키가이샤 | 고체 형태 폴리메틸알루미녹산 조성물 및 이의 제조방법 |
KR20140138337A (ko) * | 2012-03-28 | 2014-12-03 | 토소 화인켐 가부시키가이샤 | 작은 입자 직경을 갖는 고체상 폴리메틸알루미녹산 조성물의 제조방법 |
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AU624219B2 (en) | 1989-02-16 | 1992-06-04 | Idemitsu Kosan Company Limited | Process for preparation of aluminoxane |
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2020
- 2020-09-29 KR KR1020200126987A patent/KR20210038391A/ko not_active Application Discontinuation
- 2020-09-29 CN CN202080058203.XA patent/CN114269795B/zh active Active
- 2020-09-29 EP EP20871977.3A patent/EP4001314A4/de active Pending
- 2020-09-29 US US17/634,721 patent/US20220275113A1/en active Pending
- 2020-09-29 WO PCT/KR2020/013380 patent/WO2021066550A1/ko unknown
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Also Published As
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KR20210038391A (ko) | 2021-04-07 |
CN114269795B (zh) | 2024-06-21 |
US20220275113A1 (en) | 2022-09-01 |
CN114269795A (zh) | 2022-04-01 |
EP4001314A1 (de) | 2022-05-25 |
EP4001314A4 (de) | 2022-09-14 |
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